CN114534722A - Noble metal catalyst for hydrogen production from methanol, preparation method and application thereof - Google Patents
Noble metal catalyst for hydrogen production from methanol, preparation method and application thereof Download PDFInfo
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- CN114534722A CN114534722A CN202210305552.8A CN202210305552A CN114534722A CN 114534722 A CN114534722 A CN 114534722A CN 202210305552 A CN202210305552 A CN 202210305552A CN 114534722 A CN114534722 A CN 114534722A
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- methanol
- hydrotalcite
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 213
- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000001257 hydrogen Substances 0.000 title claims abstract description 73
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 73
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 73
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 64
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 64
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 38
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 32
- 239000006185 dispersion Substances 0.000 claims abstract description 18
- 229910001868 water Inorganic materials 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 13
- 238000011068 loading method Methods 0.000 claims abstract description 12
- 238000010494 dissociation reaction Methods 0.000 claims abstract description 11
- 230000005593 dissociations Effects 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 230000009467 reduction Effects 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 34
- 239000000843 powder Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 20
- 238000005303 weighing Methods 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 16
- 238000011065 in-situ storage Methods 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000001651 catalytic steam reforming of methanol Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000010970 precious metal Substances 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 50
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 24
- 229910002091 carbon monoxide Inorganic materials 0.000 description 24
- 239000011701 zinc Substances 0.000 description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910052733 gallium Inorganic materials 0.000 description 7
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- -1 Al2O3 Chemical class 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 150000002471 indium Chemical class 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000003057 platinum Chemical class 0.000 description 4
- 238000000629 steam reforming Methods 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- RLNMYVSYJAGLAD-UHFFFAOYSA-N [In].[Pt] Chemical compound [In].[Pt] RLNMYVSYJAGLAD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/007—Mixed salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a noble metal catalyst for preparing hydrogen from methanol, a preparation method and application thereof. The noble metal methanol hydrogen production catalyst comprises a carrier, an active component and an auxiliary agent, wherein the carrier is hydrotalcite LDH or roasted hydrotalcite LDO, the active component is noble metal, and the loading capacity of the noble metal is 0.05-2% based on mass percentage; the loading capacity of the auxiliary agent is 0.5% -10%; the particle size of the carrier is 5-500 nm. The invention takes ultrathin layered hydrotalcite as a carrier, carries noble metal to realize atomic-level high dispersion, and adjusts and controls the interaction such as electron transfer between active metal and the carrier by adding an auxiliary agent, increases the dissociation site of water, realizes the atomic-level dispersion solid-carrying of the active component noble metal, and has good high-temperature methanol hydrogen production performance and low CO selectivity.
Description
Technical Field
The invention belongs to the technical field of catalysts, particularly relates to the technical field of methanol hydrogen production catalysts, and more particularly relates to a noble metal methanol hydrogen production catalyst, and a preparation method and application thereof.
Background
The methanol is used as an organic liquid phase hydrogen carrier, and can realize on-line in-situ hydrogen production. The methanol steam reforming hydrogen production (MSR) has mild reaction temperature and high hydrogen yield, and is an advantageous selection route for hydrogen production. The catalyst is the key for methanol reforming hydrogen production, and noble metals such as Pt, Pd, Ru and the like can be used as active metals for cracking methanol, have excellent catalytic performance, and are the key points of research. The supports currently used are metal oxides, such as Al2O3、CeO2ZnO and SiO2The catalyst has larger specific surface area and stability, can form an intermetallic compound-oxide interface of an intermetallic phase with active metal, can carry out electron transfer with the active metal, and increases the interaction between the active metal and a carrier, thereby improving the catalytic performance, and can completely convert methanol to generate hydrogen-rich gas at a certain temperature. However, the existing research shows that the noble metal-metal oxide catalyst lacks water dissociation sites, so that the reaction temperature is higher, the methanol cracking reaction is mainly carried out, only a small amount of water participates in the reaction, and the CO concentration in the hydrogen-rich product gas is high, so that the catalyst needs to be modified and modified by adding an auxiliary agent, the dissociation of water is promoted, the CO concentration in the tail gas is reduced, and the middle and downstream CO removal is facilitated.
The common preparation method of the industrial catalyst generally comprises an impregnation method and a coprecipitation method, the operation is simple, but the load uniformity and the active metal dispersity are difficult to control. The hydrotalcite (LDH) compound is a layered double-hydroxyl composite metal oxide, a lamellar material is formed by divalent metal cations, trivalent metal cations and anions through coprecipitation, the preparation method is simple, the proportion of the compositions in the layer is adjustable, the hydrotalcite compound has a memory effect, and the loaded metal elements are uniformly and orderly dispersed in a hydrotalcite carrier in an atomic level due to the larger specific surface area and a two-dimensional lamellar structure, so that the dispersion degree of active metals is improved, and the stability of the catalyst is improved. A great deal of research finds that the addition of auxiliary agents such as alkaline earth metals, lanthanide metals and the like can improve the MSR activity of methanol, in addition, boron series metals generally show a valence of +3 in compounds, can be combined with +2 valence metal ions to form a hydrotalcite structure, and can highly disperse precious metals, so that the catalyst can maintain a low CO concentration in the hydrogen-rich gas of the product at a high temperature.
Patent CN106799228A discloses a catalyst for hydrogen production by methanol reforming, which uses CeO as catalyst2And one or more of oxides of Fe, La, Zr, Mg and Al as a carrier, and 8% of Pt and 15% of In are loaded2O3As a catalyst, the catalyst has higher conversion rate and lower CO selectivity in the high-temperature methanol hydrogen production reaction, but pungent odor is generated in the catalyst preparation process, the Pt loading capacity is higher, and the catalyst stability is still to be improved.
In the "Hydrogen production over high level active Pt based catalyst catalysis by steam reforming of methane: Effect of sub and co-sub" International Journal of Hydrogen Energy 2020,1658-1670, 15% Pt/15% In is used2O3/CeO2The catalyst has high stability, but has high Pt loading and low dispersity.
From the above, the noble metal catalyst for preparing hydrogen from methanol in the prior art has the problems of high noble metal loading, low dispersity, higher reaction temperature caused by lack of water dissociation sites, and high CO concentration in hydrogen-rich product gas.
The present invention has been made to solve the above problems.
Disclosure of Invention
The invention aims to provide a high-efficiency catalyst for preparing hydrogen from methanol, which is a preparation method of a catalyst for preparing hydrogen from ultrathin layered hydrotalcite, wherein noble metal is supported to realize high atomic-level dispersion, and the dissociation sites of water are increased by adding an auxiliary agent to regulate the interaction such as electron transfer between active metal and a carrier. The method provides a preparation method of a catalyst with high dispersion degree of noble metals such as Pt and the like, the catalyst takes at least one of Co, Ca, Zr, Mo, Zn, Ni, Mn and Mg and at least one of Ti, Mn, Ru, In, Cd, Al, Fe and Ga as hydrotalcite-like layer plate cations to form a hydrotalcite-like structure, and the performance of the catalyst is improved by changing the ratio of divalent metal to trivalent metal ions (3:1, 2:1, 1:1 and the like); by adding NaOH and Na2CO3、NaHCO3、K2CO3KOH, urea, LiOH. H2One or more of O, ammonia water and the like are used as a precipitator of hydrotalcite, the pH value of the solution is adjusted to 10-11, the morphology of the hydrotalcite is regulated and controlled by controlling the crystallization time (3-20h), and the grain size and the layer number of the hydrotalcite are controlled by combining post-treatment modes such as adding organic solvent (such as ethanol) for washing and the like; and drying and roasting to obtain carrier powder. The active metal is at least one of noble metals of subgroup VIII, such as Pt, Pd, Ru, Rh, etc., the loading is 0.05-2%, the loading is low, and atomic-level dispersion can be realized; in, Mo and the like are added as auxiliary agents, so that the dispersion of noble metals can be assisted, the dissociation of water can be promoted, and the addition amount is 0.5-10%; and carrying out in-situ reduction after calcination, and filling the obtained catalyst into a fixed bed for methanol steam reforming hydrogen production reaction.
Compared with the traditional liquid phase impregnation method, the particle size of the hydrotalcite nano-particles obtained by the method is 50-500nm, the hydrotalcite lamella is extremely thin, and Ga is added3+The plasma metal ions are bifunctional metal particles, not only serve as hydrotalcite matrix metal, but also serve as an auxiliary agent of the methanol hydrogen production catalyst, atomic-level dispersion and immobilization of active component noble metal are achieved, high-temperature methanol hydrogen production performance is good, and CO selectivity is low.
The invention provides a noble metal catalyst for preparing hydrogen from methanol, which is characterized by comprising a carrier, an active component and an auxiliary agent, wherein the carrier is hydrotalcite LDH or roasted hydrotalcite LDO after roasting, the active component is noble metal, and the loading amount of the noble metal is 0.05-2% based on mass percentage; the loading capacity of the auxiliary agent is 0.5-10%; the particle size of the carrier is 5-500 nm.
Preferably, the active component is a noble metal of subgroup VIII, selected from, but not limited to, one or more of Pt, Pd, Ru, Rh; the auxiliary agent is selected from one or more of In and Mo.
In a second aspect of the present invention, there is provided a method for preparing a catalyst for producing hydrogen from noble metal methanol according to the first aspect of the present invention, wherein the method for preparing the carrier comprises the following steps:
(1) preparing a first alkali solution;
(2) preparation of divalent Metal M12+Solution and trivalent metal M23+Dropwise adding the solution and the filtrate into the first alkali solution obtained in the step (1) to obtain a first mixture;
(3) preparing a second alkali solution, dropwise adding the second alkali solution into the first mixture obtained in the step (2), keeping the pH value of the first mixture at 9.5-11.5 after dropwise adding, and gradually precipitating hydrotalcite nano particles to obtain a second mixture;
(4) stirring and crystallizing the second mixture at room temperature for 5-30 h, filtering to obtain solid powder, washing the solid powder with deionized water and/or an organic solvent until the pH value is close to neutral, and drying to obtain a hydrotalcite LDH carrier, which is marked as M12+M23 +-LDH solid powder;
(5) obtaining the calcined hydrotalcite LDO carrier after the hydrotalcite LDH carrier is calcined, and marking as M12+M23+-LDO solid powder.
Preferably, in the step (1), the concentration of the first alkali solution is 0.1-1M.
Preferably, in step (2), M12+Selected from Co2+、Ca2+、Zr2+、Mo2+、Zn2+、Ni2+、Mn2+Or Mg2+One or more of (a); m23+Selected from Mn3+、Ru3+、In3+、Cd3+、Al3+、Fe3+Or Ga3+One or more of (a); wherein the soluble divalent metal M12+The concentration of the solution is 0.5-0.75M, and the soluble trivalent metal M23+The concentration of the solution is 0.25-0.5M; wherein the molar ratio of the divalent metal to the trivalent metal is (3-1): 1.
Preferably, in step (1) and step (3), the first alkali solution or the second alkali solution is selected from NaOH and Na2CO3、NaHCO3、K2CO3KOH, urea, LiOH. H2At least one or more of O; the concentration of the second alkali solution is 2.0-5.0M.
Preferably, in the step (4), the drying temperature is 40-70 ℃ and the drying time is 6-48 h. More preferably, the washing process in this step is washing with deionized water and then washing with an organic solvent, wherein the organic solvent is ethanol. The introduction of organic solution washing in this step is very important to the catalytic performance of the final noble metal methanol hydrogen production catalyst product, which is also a point not anticipated by this application. As can be seen from the comparison between example 1 and example 4 in the specific embodiment of the present invention, the catalyst prepared in example 1 by washing the particles with deionized water until the pH is nearly neutral and then washing the particles with 400mL of ethanol for a further 2 hours, whereas example 4 by washing with only deionized water and without using ethanol as an organic solvent, the catalyst prepared in both cases was used in the hydrogen production reaction by steam reforming of methanol, the methanol conversion rate of example 1 was 99%, whereas the methanol conversion rate of example 4 was only 75.6%, which are far from each other, and the CO of example is very different from each other2The selectivity is also more excellent.
Preferably, in the step (5), the calcination is carried out in an air atmosphere, the calcination temperature is 300-500 ℃, and the calcination time is 2-10 h.
Preferably, the noble metal methanol hydrogen production catalyst loaded with noble metal and auxiliary agent is prepared by a co-impregnation method, and the method specifically comprises the following steps:
(A) preparing a soluble precious metal salt organic solution and a soluble auxiliary agent salt organic solution;
(B) weighing the hydrotalcite LDH carrier or the roasted hydrotalcite LDO carrier prepared by the method, pouring the hydrotalcite LDH carrier or the roasted hydrotalcite LDO carrier into 3-100 mL of deionized water, transferring a proper amount of noble metal solution and auxiliary agent solution, dropwise adding the noble metal solution and the auxiliary agent solution, stirring at room temperature, drying in vacuum, and calcining to obtain the noble metal methanol hydrogen production catalyst.
Preferably, in the step (A), the concentration of the noble metal is 0.05-0.2M; the concentration of the auxiliary metal is 0.1-1M; the organic solvent is selected from ethanol.
Preferably, in the step (A), stirring is carried out for 1-8h at room temperature, the vacuum drying temperature is 40-70 ℃, the drying time is 4-24 h, the calcination temperature is 350-.
In a third aspect, the invention provides an application of the noble metal catalyst for methanol hydrogen production according to the first aspect of the invention, and the noble metal catalyst is used as a catalyst in a methanol hydrogen production reaction.
Preferably, the catalyst is filled into a fixed bed reactor for in-situ reduction and then methanol steam reforming hydrogen production reaction is carried out, the MSR is operated at normal pressure, the reaction temperature is 280-400 ℃, the water-carbon ratio is 1-3, and the mass airspeed of methanol is 1.5-3 h-1. More preferably, the reaction temperature is 360 ℃, the water-carbon ratio is 1, and the mass space velocity is 1.5h-1。
Preferably, before use, the noble metal catalyst for preparing hydrogen from methanol is loaded into a fixed bed for in-situ reduction, the reduction temperature is 200-450 ℃, the reduction time is 1-4H, and the reduction atmosphere is 5-50% of H2/N2And (4) mixing the gases.
The fourth aspect of the invention provides a method for improving the dispersion degree of active components in a noble metal methanol hydrogen production catalyst, and the hydrotalcite LDH prepared by the preparation method of the second aspect of the invention or the roasted hydrotalcite LDO after roasting is selected as a carrier.
The invention provides a method for reducing the concentration of CO in the hydrogen of the reaction product of the methanol hydrogen production, which uses the noble metal catalyst of the first aspect of the invention as a reaction catalyst, wherein the noble metal catalyst of the methanol hydrogen production uses hydrotalcite LDH or roasted hydrotalcite LDO after roasting as a carrier, and the noble metal catalyst of the methanol hydrogen production also contains an auxiliary agent to increase the dissociation site of water in the catalyst.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention takes ultrathin layered hydrotalcite as a carrier, carries noble metal to realize atomic-level high dispersion, and adjusts and controls the interaction such as electron transfer between active metal and the carrier by adding an auxiliary agent, increases the dissociation site of water, realizes the atomic-level dispersion solid-carrying of the active component noble metal, and has good high-temperature methanol hydrogen production performance and low CO selectivity.
2. In the preparation process of the noble metal methanol hydrogen production catalyst, M1 is directly used2+And M23+Especially Zn2+And Ga3+The metal ions are used as matrix metals to directly form a hydrotalcite two-dimensional laminate structure, hydrotalcite has the structural characteristic of stable structure, and the laminate metal structure can carry out lattice constraint and directional isolation on noble metals and auxiliary metal, so that the noble metals can be further dispersed at atomic level under the action of the auxiliary. After subsequent high-temperature roasting and reaction, the dispersion and immobilization state of the noble metal and the auxiliary agent can still be maintained, surface migration is rarely generated, the structure is stable, and the atomic-level dispersion and immobilization of the active component noble metal is realized. In addition M12+And M23+The base metal and the auxiliary metal can form specific electron transfer or combined action with the noble metal of the active component to different degrees, such as forming alloy solid solution. The characteristics enable the specific surface area and the acidity and alkalinity of the noble metal catalyst to be regulated and controlled, thereby improving the selectivity of the methanol steam reforming reaction, reducing the CO concentration, having high-temperature stability and effectively inhibiting the formation of carbon deposition.
3. Specifically, cations such as 3-valent Ga are adopted as bifunctional metal ions, and the bifunctional metal ions can be directly used as hydrotalcite laminate plates and can also be used as auxiliary agents. The hydrotalcite technology and the modification effect of the In, Ga and other auxiliary agents are adopted, so that the noble metal atomic-level high dispersion can be realized, and the dissociation of water can be promoted. The type concentration and the adding rate of the alkali, the constant temperature crystallization method and the post-treatment method can regulate and control the thickness of the hydrotalcite sheet layer. Due to comprehensive reasons, the noble metal catalyst for preparing hydrogen from methanol has good hydrogen preparation performance and excellent CO inhibition effect, can greatly reduce the selectivity of CO, and can obtain hydrogen-rich gas with low CO concentration.
4. According to the noble metal catalyst for preparing hydrogen from methanol, which is disclosed by the invention, XRD analysis can be used for characterizing that a catalyst precursor is metal oxide hydrotalcite, an SEM (figure 1) is used for observing an ultrathin and ultra-small nanosheet layer of the hydrotalcite, a TEM (figure 2) is used for observing the ultrathin nanosheet layer, nanoclusters are not observed, and the dispersity is good, so that the ZnGa hydrotalcite can enable Pt to achieve atomic-scale dispersion by adding an In auxiliary agent.
5. The catalyst prepared by the invention is used for methanol steam reforming hydrogen production reaction by preparing a reaction furnace device with a quartz tube with gas flow control, the conversion rate of reactants is 70-99.9%, the CO selectivity is lower than 6%, and after the unsteady reaction is carried out for 72h, the catalytic performance is not changed greatly and the catalyst can be recycled. By taking a noble metal catalyst prepared by a traditional solution impregnation method and a noble metal catalyst taking Zn as an auxiliary agent as references, the conversion rate of the methanol steam hydrogen production reaction is 60-90 percent under the same condition, but the CO selectivity is 60-90 percent, the catalyst has a small amount of carbon deposition phenomenon, and the recycling performance is reduced.
6. In the preparation process of the carrier of the noble metal catalyst for preparing hydrogen from methanol, the washing process of the step (4) introduces organic solution for washing, which is very important for the catalytic performance of the final noble metal catalyst product for preparing hydrogen from methanol, and is also one unexpected point in the application. As can be seen from the comparison between example 1 and example 4 in the specific embodiment of the present invention, the catalyst prepared in example 1 by washing the particles with deionized water until the pH is nearly neutral and then washing the particles with 400mL of ethanol for a further 2 hours, whereas example 4 by washing with only deionized water and without using ethanol as an organic solvent, the catalyst prepared in both cases was used in the hydrogen production reaction by steam reforming of methanol, the methanol conversion rate of example 1 was 99%, whereas the methanol conversion rate of example 4 was only 75.6%, which are far from each other, and the CO of example is very different from each other2The selectivity is also more excellent.
Drawings
FIG. 1 is a scanning electron micrograph SEM of the hydrotalcite lamellar structures employed in examples 1 to 3;
FIG. 2 is a TEM image of the Pt hydrotalcite employed in example 1, showing the particle size lattice and degree of dispersion;
FIG. 3 is an XRD spectrum of examples 1-3.
Detailed Description
The present invention will be described below with reference to specific examples, but the embodiments of the present invention are not limited thereto. The experimental methods not specified in the examples are generally commercially available according to the conventional conditions and the conditions described in the manual, or according to the general-purpose equipment, materials, reagents and the like used under the conditions recommended by the manufacturer, unless otherwise specified. The starting materials required in the following examples and comparative examples are all commercially available.
Example 1:
first, 2.6g of Na was weighed2CO3Dissolving in 50mL of deionized water to prepare 0.5M Na2CO3A solution; taking the ratio of Zn to Ga as Zn: ga 3:1 (mol: mol), 11.2g of Zn (NO) was weighed out3)2·6H2O and 3.2g Ga nitrate were dissolved in 50mL deionized water to make 0.75M Zn2+Solution and 0.25M Ga3+The solution is gradually added dropwise to the Na2CO3In solution; weighing 6.4g of NaOH and dissolving the NaOH in 40mL of deionized water to prepare 4M NaOH solution, dropwise adding the NaOH solution into the metal mixed solution to keep the pH value at 10, and gradually precipitating hydrotalcite nano particles; a crystallization process, stirring for 17h at room temperature, filtering the suspension, washing the particles with deionized water until the pH value is close to neutral, further washing with 400mL of ethanol for 2h, and drying the separated solid matter in a vacuum drying oven for 8h to obtain ZnGa-LDH white solid powder; calcining the solid powder for 6 hours at 450 ℃ in an air atmosphere to obtain ZnOGa2O3-LDO white solid powder.
Weighing a certain amount of platinum salt and indium salt to prepare 0.12M and 0.5M organic solvent solutions, weighing a certain amount of ZnGa-LDO carrier obtained In the step one, adding the ZnGa-LDO carrier into a platinum-indium organic solvent, stirring for 4h at room temperature, drying for 6h at 40 ℃ In vacuum, calcining the dried solid powder In air at 450 ℃ for 6h to obtain Pt @ In2O3/Zn3Ga-LDO catalyst; before use, the solid powder is put into a fixed bed for in-situ reduction, the reduction temperature is 400 ℃, the reduction time is 2H, and the reduction atmosphere is 50 percent of H2/N2And (4) mixing the gases.
Confirmation of M1 by XRD characterization2+M23+And (4) forming an LDO hydrotalcite structure, and observing the particle size of the LDO hydrotalcite to be 5-500nm through SEM and TEM characterization, wherein the appearance is a two-dimensional thin sheet layer structure.
Example 2:
example 2 was compared with example 1, except that the ratio of zinc to gallium was 2: 1.
First, 2.6g of Na was weighed2CO3Dissolving in 50mL of deionized water to prepare 0.5M Na2CO3A solution; taking the ratio of Zn to Ga as Zn: ga 2:1 (mol: mol), 10.4g of Zn (NO) was weighed out3)2·6H2O and 3.8g Ga nitrate were dissolved in 50mL deionized water to prepare 0.7M Zn2+Solution and 0.3M Ga3+The solution is gradually and dropwise added to the Na2CO3In solution; weighing 6.4g of NaOH and dissolving the NaOH in 40mL of deionized water to prepare 4M NaOH solution, dropwise adding the NaOH solution into the metal mixed solution to keep the pH value at 10, and gradually precipitating hydrotalcite nanoparticles; the crystallization process was then carried out, stirring at room temperature for 17h, filtering the suspension and washing the particles with deionized water to a pH close to neutral, followed by a further 2h wash with 400mL ethanol. Putting the solid matter obtained by separation into a vacuum drying oven for drying for 8 hours to obtain ZnGa-LDH white solid powder; calcining the solid powder for 6 hours at 450 ℃ in an air atmosphere to obtain ZnOGa2O3-LDO white solid powder.
Weighing a certain amount of platinum salt and indium salt to prepare 0.12M and 0.5M organic solvent solutions, weighing a certain amount of ZnGa-LDO carrier obtained In the step one, adding the ZnGa-LDO carrier into a platinum-indium organic solvent, stirring for 4h at room temperature, drying for 6h at 40 ℃ In vacuum, calcining the dried solid powder In air at 450 ℃ for 6h to obtain Pt @ In2O3/Zn2Ga-LDO catalyst; before use, the solid powder is put into a fixed bed for in-situ reduction, the reduction temperature is 400 ℃, the reduction time is 2H, and the reduction atmosphere is 50 percent of H2/N2And (4) mixing the gases.
Example 3:
example 3 was compared with examples 1 and 2, except that the ratio of zinc to gallium was 1: 1.
First, 2.6g of Na was weighed2CO3Dissolving in 50mL of deionized water to prepare 0.5M Na2CO3A solution; taking the ratio of Zn to Ga as Zn: ga 1:1 (mol: mol), 7.4g of hydrated zinc nitrate and 6.4g of hydrated gallium nitrate were weighed and dissolved in 50mL of deionized water to prepare 0.5M Zn2+Solution and 0.5M Ga3+A solution; weighing 6.4g of NaOH and dissolving the NaOH in 40mL of deionized water to prepare 4M NaOH solution, dropwise adding the NaOH solution into the metal mixed solution to keep the pH value at 10, and gradually precipitating hydrotalcite nanoparticles; the crystallization process was then carried out, stirring at room temperature for 17h, filtering the suspension and washing the particles with deionized water to a pH close to neutral, followed by a further 2h wash with 400mL ethanol. Putting the solid matter obtained by separation into a vacuum drying oven for drying for 8 hours to obtain ZnGa-LDH white solid powder; calcining the solid powder for 6 hours at 450 ℃ in an air atmosphere to obtain ZnOGa2O3-LDO white solid powder.
Weighing a certain amount of platinum salt and indium salt to prepare 0.12M and 0.5M organic solvent solutions, weighing a certain amount of ZnGa-LDO carrier obtained In the step one, adding the ZnGa-LDO carrier into a platinum-indium organic solvent, stirring for 4h at room temperature, drying for 6h at 40 ℃ In vacuum, calcining the dried solid powder In air at 450 ℃ for 6h to obtain Pt @ In2O3/Zn1Ga-LDO catalyst; before use, the solid powder is put into a fixed bed for in-situ reduction, the reduction temperature is 400 ℃, the reduction time is 2H, and the reduction atmosphere is 50 percent of H2/N2And (4) mixing the gases.
Example 4:
example 4 was compared with example 1, except that only deionized water was used as the solvent for washing, and no organic solvent was used, in preparing the hydrotalcite precursor, in order to compare the effects of the organic solvent and water. The other steps are consistent. Obtaining Pt @ In2O3/Zn3Ga(H2O) a catalyst.
Example 5:
the embodiment 5 is compared with the embodiment 1, except that the prepared hydrotalcite precursor is not calcined, and is directly loaded with active metal and auxiliary agent after being dried, and then is calcined. And other steps are consistent. Obtaining Pt @ In2O3/Zn3Ga (LDH) catalyst.
Example 6:
example 6 was compared with example 1, except that the In adjuvant was not contained. Obtaining Pt/Zn3Ga-LDO catalyst.
Comparative example 1:
to compare the catalyst performance of the samples, we used commercial alumina as the support and impregnated Pt salt to commercial Al using an impregnation method2O3On a carrier. Weighing a certain amount of chloroplatinic acid to prepare a solution, and weighing Al with the same mass as that in the example2O3Slowly adding the carrier into the solution, stirring at room temperature for 4h, drying at 40 ℃ for 6h under vacuum, calcining the dried solid powder in air at 450 ℃ for 6h to obtain Pt @ Al2O3A catalyst; before use, the solid powder is put into a fixed bed for in-situ reduction, the reduction temperature is 400 ℃, the reduction time is 2H, and the reduction atmosphere is 50 percent of H2/N2And (4) mixing the gases. The loading of Pt was 0.5%.
Comparative example 2:
to compare the catalyst performance of the samples, we co-impregnated Pt salt and Zn promoter to commercial Al using an impregnation method using commercial alumina as the support2O3On a carrier. Weighing a certain amount of chloroplatinic acid and zinc nitrate to prepare a solution, and weighing a certain amount of industrial Al2O3Slowly adding the carrier into the solution, stirring at room temperature for 4h, drying at 40 ℃ for 6h under vacuum, calcining the dried solid powder in air at 450 ℃ for 6h to obtain PtZn @ Al2O3A catalyst; before use, the solid powder is put into a fixed bed for in-situ reduction, the reduction temperature is 400 ℃, the reduction time is 2H, and the reduction atmosphere is 50 percent of H2/N2And (4) mixing the gases.
Comparative example 3:
to compare the catalytic properties of the samplesThe method can adopt industrial alumina as a carrier to carry out ZnAl hydrotalcite in-situ growth on the alumina carrier to obtain the ZnAl-LDH carrier. Weighing a certain amount of chloroplatinic acid to prepare a solution, weighing a certain amount of ZnAl-LDH carrier, slowly adding the ZnAl-LDH carrier into the solution, stirring for 4h at room temperature, drying for 6h at 40 ℃ in vacuum, calcining the dried solid powder in air at 450 ℃ for 6h to obtain Pt @ ZnAl2O3-an LDO catalyst; before use, the solid powder is put into a fixed bed for in-situ reduction, the reduction temperature is 400 ℃, the reduction time is 2H, and the reduction atmosphere is 50 percent of H2/N2And (4) mixing the gases.
Comparative example 4:
in order to compare the catalyst performance of samples, industrial alumina is adopted as a carrier, and ZnAl hydrotalcite is grown in situ on the alumina carrier to obtain a ZnAl-LDH carrier. Weighing a certain amount of platinum salt and indium salt to prepare a solution, weighing a certain amount of ZnAl-LDH carrier, slowly adding the ZnAl-LDH carrier into the solution, stirring for 4h at room temperature, drying for 6h at 40 ℃ in vacuum, calcining the dried solid powder in air at 450 ℃ for 6h to obtain Pt @ ZnAl2O3-an LDO catalyst; before use, the solid powder is put into a fixed bed for in-situ reduction, the reduction temperature is 400 ℃, the reduction time is 2H, and the reduction atmosphere is 50 percent of H2/N2And (4) mixing the gases.
Application examples 1 to 10:
the methanol steam reforming hydrogen production catalysts prepared in examples 1 to 6 and comparative examples 1 to 4 were subjected to performance evaluation of methanol steam reforming hydrogen production by a miniature fixed bed reaction apparatus, the reaction was carried out at normal pressure, and when the reaction temperature was 360 ℃, the ratio of methanol to water in the raw materials was 1: 1(mol/mol), the raw material feeding flow is 8mL/h, and nitrogen is used as carrier gas in the reaction process.
The results of the characterization analysis of the reaction products of examples 1 to 6 and comparative examples 1 to 4 are shown in Table 1, and mainly include the conversion rate of methanol (MeOH), carbon monoxide (CO), and carbon dioxide (CO)2) And (4) selectivity.
TABLE 1 Performance of hydrogen production by steam reforming of methanol in examples 1 to 6 and comparative examples 1 to 4
As can be seen from the table, the methanol steam reforming hydrogen production catalyst prepared by the invention can effectively reduce the selectivity of CO. The catalyst in example 1 catalyzed a methanol conversion of 99% with a CO selectivity of 4.1%. Under the same conditions, reducing the amount of Zn leads to a decrease in methanol conversion, proving the best effect at a ZnGa molar ratio of 3: 1. The conversion rates of methanol obtained In comparative example 1 and comparative example 2 are 90% and 77%, respectively, and the selectivity of CO is as high as 89% and 78%, which shows that the In and Ga auxiliary agents have great promotion effects on Pt dispersion and water dissociation, and can greatly reduce the selectivity of CO.
A comparison of examples 1 to 3 shows that the ratio of zinc to gallium has a greater influence on the methanol conversion, with example 1 having a ratio of zinc to gallium of 3:1 of Pt @ In2O3/Zn3The methanol conversion rate of the Ga-LDO reaches up to 99 percent. The comparison between example 1 and example 4 shows that the choice of the solvent for washing is also critical when preparing the hydrotalcite precursor, and the catalyst prepared by washing with deionized water and then with ethanol in example 1 has more excellent performance. As can be seen from the comparison between example 1 and example 5, the catalyst prepared by the calcined hydrotalcite LDO carrier obtained by calcination has more excellent catalytic performance. As can be seen from the comparison between example 1 and example 6, the addition of the In promoter is beneficial to improving the methanol conversion rate and CO2And (4) selectivity. According to the data of the practical comparison 3-4, the ZnAl-LDH carrier is obtained by carrying out ZnAl hydrotalcite in-situ growth on the alumina carrier, which is different from the hydrotalcite carrier prepared by the preparation method, and the finally obtained noble metal catalyst for preparing hydrogen from methanol has excellent catalytic performance.
The catalyst prepared by the method has better hydrothermal stability, and tests show that the water-carbon ratio is increased and the methanol conversion rate is reduced less by changing the raw materials.
The above embodiments describe the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited by the embodiments described above, which are given by way of illustration of the principles of the invention and are not to be taken as limiting the scope of the invention in any way, and that various changes and modifications may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (10)
1. The catalyst for preparing hydrogen from methanol by using noble metal is characterized by comprising a carrier, an active component and an auxiliary agent, wherein the carrier is hydrotalcite LDH or roasted hydrotalcite LDO after roasting, the active component is noble metal, and the loading amount of the noble metal is 0.05-2% based on mass percentage; the loading capacity of the auxiliary agent is 0.5-10%; the particle size of the carrier is 5-500 nm.
2. The noble metal catalyst for methanol hydrogen production according to claim 1, wherein the active component is noble metal of subgroup VIII selected from one or more of Pt, Pd, Ru and Rh; the auxiliary agent is selected from one or more of In and Mo.
3. A method for preparing a noble metal catalyst for methanol hydrogen production according to any one of claims 1-2, wherein the method for preparing the carrier comprises the following steps:
(1) preparing a first alkali solution;
(2) preparation of divalent Metal M12+Solution and trivalent metal M23+Dropwise adding the solution and the filtrate into the first alkali solution obtained in the step (1) to obtain a first mixture;
(3) preparing a second alkali solution, dropwise adding the second alkali solution into the first mixture obtained in the step (2) to keep the pH value of the first mixture at 9.5-11.5, and gradually precipitating hydrotalcite nano particles to obtain a second mixture;
(4) stirring and crystallizing the second mixture at room temperature for 5-30 h, filtering to obtain solid powder, washing the solid powder to neutrality by using deionized water and/or an organic solvent, and drying to obtain a hydrotalcite LDH carrier, wherein the carrier is marked as M12+M23+-LDH solid powder;
(5) obtaining the calcined hydrotalcite LDO carrier after the hydrotalcite LDH carrier is calcined, and marking as M12+M23+-LDO solid powder.
4. The production method according to claim 3, characterized in that, in the step (1), the concentration of the first alkali solution is 0.1 to 1M;
in step (2), M12+Selected from Co2+、Ca2+、Zr2+、Mo2+、Zn2+、Ni2+、Mn2+Or Mg2+One or more of (a); m23+Selected from Mn3+、Ru3+、In3+、Cd3+、Al3+、Fe3+Or Ga3+One or more of (a); wherein the soluble divalent metal M12+The concentration of the solution is 0.5-0.75M, and the soluble trivalent metal M23+The concentration of the solution is 0.25-0.5M; wherein the molar ratio of the divalent metal to the trivalent metal is (3-1): 1; .
In the step (1) and the step (3), the first alkali solution or the second alkali solution is selected from NaOH and Na2CO3、NaHCO3、K2CO3KOH, urea, LiOH. H2At least one or more of O; the concentration of the second alkali solution is 2.0-5.0M;
in the step (4), the drying temperature is 40-70 ℃, and the drying time is 6-48 h; the washing process is that the washing is firstly carried out by deionized water and then is carried out by an organic solvent;
in the step (5), the roasting is carried out in an air atmosphere, the roasting temperature is 300-500 ℃, and the roasting time is 2-10 h.
5. The preparation method according to any one of claims 3 to 4, wherein the preparation of the noble metal methanol hydrogen production catalyst loaded with the noble metal and the auxiliary agent by using a co-impregnation method comprises the following steps:
(A) preparing a soluble precious metal salt organic solution and a soluble auxiliary agent salt organic solution;
(B) weighing the hydrotalcite LDH carrier or the roasted hydrotalcite LDO carrier prepared by the preparation method of any one of claims 3 to 4, pouring the weighed hydrotalcite LDH carrier or the roasted hydrotalcite LDO carrier into 3-100 mL of deionized water, transferring the noble metal solution and the auxiliary agent solution, dropwise adding the noble metal solution and the auxiliary agent solution, stirring at room temperature, drying in vacuum, and calcining to obtain the noble metal methanol hydrogen production catalyst.
6. The method according to claim 5, wherein in the step (A), the concentration of the noble metal is 0.05 to 0.2M; the concentration of the assistant metal is 0.1-1M; the organic solvent is selected from ethanol;
in the step (B), stirring for 1-8h at room temperature, wherein the vacuum drying temperature is 40-70 ℃, the drying time is 4-24 h, the calcining temperature is 350-500 ℃, and the calcining time is 2-12 h.
7. Use of a noble metal catalyst for methanol hydrogen production according to any one of claims 1-2 as a catalyst in a methanol hydrogen production reaction.
8. The application of the catalyst of claim 7, wherein the catalyst is filled in a fixed bed reactor to carry out in-situ reduction and then carry out methanol steam reforming hydrogen production reaction, the MSR is operated at normal pressure, the reaction temperature is 280-400 ℃, the water-carbon ratio is 1-3, and the mass space velocity of methanol is 1.5-3 h-1；
Before use, the noble metal catalyst for preparing hydrogen from methanol is loaded into a fixed bed for in-situ reduction, the reduction temperature is 200-450 ℃, the reduction time is 1-4H, and the reduction atmosphere is 5-50% of H2/N2And (4) mixing the gases.
9. A method for improving the dispersion degree of active components in a noble metal catalyst for preparing hydrogen from methanol is characterized in that hydrotalcite LDH prepared by the preparation method of any one of claims 3 to 4 or roasted hydrotalcite LDO after roasting is selected as a carrier.
10. A method for reducing the CO concentration in the hydrogen of a methanol hydrogen production reaction product is characterized in that the noble metal methanol hydrogen production catalyst as claimed in any one of claims 1 to 2 is used as a reaction catalyst, the noble metal methanol hydrogen production catalyst adopts hydrotalcite LDH or roasted hydrotalcite LDO after roasting as a carrier, and the noble metal methanol hydrogen production catalyst also contains an auxiliary agent so as to increase the dissociation sites of water in the catalyst.
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